EP1321448A1 - Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik - Google Patents

Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik Download PDF

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Publication number
EP1321448A1
EP1321448A1 EP01870291A EP01870291A EP1321448A1 EP 1321448 A1 EP1321448 A1 EP 1321448A1 EP 01870291 A EP01870291 A EP 01870291A EP 01870291 A EP01870291 A EP 01870291A EP 1321448 A1 EP1321448 A1 EP 1321448A1
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EP
European Patent Office
Prior art keywords
ceramic
oxidic
contact angle
water
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01870291A
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English (en)
French (fr)
Inventor
René van de Leest
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vlaamse Instelling Voor Technologish Onderzoek NV VITO
Original Assignee
Vlaamse Instelling Voor Technologish Onderzoek NV VITO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vlaamse Instelling Voor Technologish Onderzoek NV VITO filed Critical Vlaamse Instelling Voor Technologish Onderzoek NV VITO
Priority to EP01870291A priority Critical patent/EP1321448A1/de
Priority to EP20020102767 priority patent/EP1321309A2/de
Priority to US10/324,638 priority patent/US20030145749A1/en
Priority to JP2002368071A priority patent/JP2003211623A/ja
Priority to PCT/BE2002/000193 priority patent/WO2003053882A1/en
Publication of EP1321448A1 publication Critical patent/EP1321448A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/0045—Irradiation; Radiation, e.g. with UV or IR
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/0072—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics

Definitions

  • the present invention is related to a method for reversibly changing the hydrophilic properties of a ceramic oxide or an oxidic ceramic.
  • the present invention is also related to a number of applications, such as a method for reversible lithographic printing using ceramics.
  • Ceramic oxides and oxidic ceramics are known materials, which are useful in numerous applications, such as a substrate for supporting electrical circuits (e.g. in semiconductor production), such as membranes or filters in a wide range of dimensions, and for artefacts resistant to high wear and temperature.
  • Ceramic materials Some of the more interesting properties of ceramic materials include their hardness and their heat resistance and thermal conductivity, which makes ceramic oxides and oxidic ceramics especially useful in applications with high but specific material requirements.
  • Ceramic oxides and oxidic ceramics can be defined as solid compounds which are usually made by sintering particles (powder) together at high temperatures to form a dense, hard and durable material. Ceramics can therefore be characterised by their specific mechanical and/or functional properties.
  • Lithographic printing plates are used for digital offset press applications.
  • the process from electronic information to printing is also described as computer-to-plate printing.
  • lithographic printing plates are light-sensitive imaging plates and thermal plates.
  • the substrate for the plates is usually anodised aluminium. These types of plates can only be used once.
  • US 5893328 discloses reusable printing material (a composite of zirconia alloy and ⁇ -alumina) that can be used to high-energy irradiation to cause localised "melting" of alloy in the exposed areas, thereby creating oleophilic surfaces.
  • reusable printing material a composite of zirconia alloy and ⁇ -alumina
  • the mechanism for the conversion between hydrophilic and oleophilic is not clear: in US 5836249 it is disclosed that local ablation and formation of substoichiometric zirconia is responsible for the conversion to oleophilic surfaces while in US 5893328 it is disclosed for exactly the same experimental conditions that local melting is the cause for oleophilic behaviour.
  • the high laser power output takes the irradiation effects into the "thermal" region where melting or decomposition might occur, thus making this process not a truly reversible process.
  • Preferred materials used in the prior art process comprise zirconia-alumina ceramic composites with a zirconia content from 50% to 99.9%.
  • Other materials named are: zirconia, alumina, zirconia composites (with MgO, CaO, Y 2 O 3 , Sc 2 O 3 and rare earth oxides), aluminium-magnesium silicate, magnesium silicate and silicon carbide.
  • Monolithic ceramics as well as ceramic layers are described.
  • the porosity of the ceramic materials must be between 0.1% and 2%.
  • the grain size should lie between 0.2 ⁇ m and 1 ⁇ m.
  • the prior art process is thus essentially a thermal process. Further, it relies on massive light doses to melt or decompose the surface. This makes the prior art process slow.
  • the prior art process is also restricted to only a few ceramic materials.
  • the intense local heating of the ceramic induces local sintering which impairs the process reversibility. Therefore the prior art process is limited to ceramic materials with inhibited grain growth such as zirconia toughened alumina.
  • the prior art process also yields surface damage through local melting or decomposition which leads to rather irreversible surface morphology changes. Therefore, it is not really a reversible process.
  • the present invention aims to provide a method for truly reversibly changing the hydrophilic properties of a ceramic oxide or an oxidic ceramic.
  • the present invention aims to provide a method for lithographic printing using reversibly imprinted printing plates.
  • a further aim of the present invention is to provide a base for the next generation digital offset printing technology based on a reversible switching between hydrophilic and oleophilic surfaces of ceramic materials.
  • the present invention concerns mainly a method for reversibly increasing the contact angle for water on a ceramic oxide or an oxidic ceramic surface, characterised in that the method comprises the step of introducing a surface defect in said surface.
  • Said step of introducing a surface defect comprises preferably a step selected from the group consisting of UV radiation with a wavelength between 200nm and 400nm and heating under low partial oxygen pressure.
  • the method of the invention is executed under low partial oxygen pressure or in a reducing atmosphere.
  • UV radiation is used, suitable light can be readily obtained with a low-pressure mercury lamp.
  • heating under low partial oxygen pressure it is preferably performed at a temperature of about 200°C or higher. Said heating under low partial oxygen pressure can be performed using a diode laser at low fluence.
  • the resulting contact angle for water is preferably higher than 20°, advantageously higher than 40°.
  • Another aspect of the present invention concerns a method for reversibly reducing the contact angle for water on a ceramic oxide or an oxidic ceramic surface obtainable by the method of the invention, characterised in that the method comprises the step of heating the surface in an oxidising atmosphere.
  • Said oxidising atmosphere is preferably air.
  • Said heating is preferably performed at about 200°C or higher.
  • the ceramic oxide or oxidic ceramic for use in the method according to the present invention is preferably selected from the group consisting of alumina, zirconia and anodised aluminium.
  • the use of the method of the invention for creating oleophilic images on a hydrophilic surface or vice versa, e.g. for lithographic printing purposes is disclosed.
  • Yet another aspect of the present invention concerns a method for treating a ceramic oxide or an oxidic ceramic substrate having a surface, comprising the step of introducing a surface defect on said surface, thereby reversibly increasing the contact angle for water.
  • Another aspect of the present invention relates to a method for lithographic printing, comprising the steps of:
  • Figure 1 shows the creation and annihilation of a surface defect according to the present invention.
  • Figure 2 represents a preferred embodiment of the present invention.
  • Figure 3 describes a lithographic printing process according to the present invention.
  • a hydrophilic surface is characterised by a contact angle equal to zero for water, while for an oleophilic surface the contact angle for water is greater than zero.
  • the reversible hydrophilic - oleophilic transition is created by changing the defect structure of the ceramic surface.
  • Surface defects at ceramic surfaces can be created by physicochemical processes such as UV-irradiation or laser irradiation at low partial oxygen pressure. Surface defects at ceramic surfaces can be annihilated by heating under large partial oxygen pressure.
  • ceramic oxides or oxidic ceramics can be used to practise the present invention. These materials must satisfy certain criteria, which can be described as:
  • the material should be electrically isolating i.e. defects, charge carriers should not diffuse and give rise to recombinations. Further, the bandgap must be greater than the formation enthalpy for oxygen vacancies (or the irradiation energy should be smaller than the bandgap)
  • Monolithic oxide ceramics such as alumina, zirconia, ... can be used to practise the present invention.
  • oxidic ceramic composites, grain boundary modified oxidic ceramics and ceramic layers on a substrate can be used.
  • Said substrate can be selected from ceramics, glasses, metals and semiconductors or the like.
  • Deposition methods include sol-gel, PVD, CVD, Plasma-based deposition and/or Laser-based deposition
  • Generation of an oleophilic surface 6 is done by creating an oleophilic ceramic surface (contact angle for water >0°), by creating surface crystal imperfections 7 such as oxygen vacancies.
  • the formation enthalpy of oxygen vacancies lies in the range 2 - 5 eV.
  • Surface defects in oxidic ceramics are created by physicochemical processes 4 such as:
  • U.V. radiation with a wavelength ⁇ between 200 and 350 nm is particularly suited to create surface defects according to the present invention.
  • a low oxygen partial pressure is preferred in order to avoid ozone production.
  • Heating under partial oxygen pressure shifts the defect equilibrium to the region where oxygen vacancies are the predominant defect species. Therefore it can also be used to practise the present invention.
  • a low partial oxygen pressure can be created by using a flow of inert gases such as nitrogen and argon....
  • a better way even is to create a reducing atmosphere by adding a reducible gas such as hydrogen.
  • the process according to this embodiment of the present invention does not provoke any local sintering or melting.
  • Example 1 Lithographic printing using reversibly imprinted printing plates
  • the reversible conversion hydrophilic /oleophilic at the surface of ceramic materials forms the basis for the printing process. Ink is retained at oleophilic surfaces and is rejected at hydrophilic surfaces. Image formation occurs by turning the surface oleophilic and image erasure is effectuated by turning the surface hydrophilic.
  • Image erasure generation of a hydrophilic surface
  • Image erasure generation of a hydrophilic surface
  • image erasure can be done by annihilation of surface defects such as oxygen vacancies by reaction with oxygen.
  • Image formation (generation of an oleophilic surface) is done by creating surface crystal imperfections such as oxygen vacancies.
  • ⁇ -alumina powder CT3000SG (Alcoa) is pressed, sintered and polished to form a ceramic artefact.
  • the surface of the alumina artefact 1 is selectively illuminated with UV irradiation 3 via a mask 2 (see figure 2 a and 2 b).
  • the irradiated surface is hydrophobic and the nonirradiated surface stays hydrophilic.
  • the surface of the anodised aluminium is selectively illuminated with UV irradiation via a mask.
  • the irradiated surface is hydrophobic and the nonirradiated surface stays hydrophilic.
  • the complete surface is sponged with water.
  • the hydrophilic surfaces retain the water, creating a homogeneous water layer.
  • the ink pattern can then be transferred to a rubber stamp, which can be used to print the pattern e.g. on paper.
  • a ceramic surface 10 substantially without surface defects is covered with a mask 12 (11).
  • the oleophilic surface 14 will retain the ink, whereas the hydrophilic surface 16 will not. This creates an ink-loaded surface 18.
  • Transfer of the ink to a rubber stamp (or directly to a support surface) (19,21) yields an ink-loaded rubber stamp 20 which can be used to print on the usual support (e.g. paper).
  • the invention can readily be applied to the creation of electrical circuits (and transistor-like structures) on ceramic substrates, orientation of liquid crystals in LCD's, self-assembly and self-alignment of structures via amphotereous molecules, ceramic membranes (filtration of water or organic materials), power cell electrodes (hydrophobic on the gas side and hydrophilic on the fluid side), pretreatment of ceramic surfaces to improve assembly of identical or different materials to each other, the creation of supports for biological molecules for detection purposes (such as biochips) , ... .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
EP01870291A 2001-12-21 2001-12-21 Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik Withdrawn EP1321448A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP01870291A EP1321448A1 (de) 2001-12-21 2001-12-21 Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik
EP20020102767 EP1321309A2 (de) 2001-12-21 2002-12-16 Verfahren zur Herstellung einer lithographischen Druckplatte
US10/324,638 US20030145749A1 (en) 2001-12-21 2002-12-19 Method for making a lithographic printing plate
JP2002368071A JP2003211623A (ja) 2001-12-21 2002-12-19 リゾグラフイーの印刷プレートを作る方法
PCT/BE2002/000193 WO2003053882A1 (en) 2001-12-21 2002-12-20 Method for reversibly changing the hydrophilic properties of a ceramic oxide or an oxidic ceramic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01870291A EP1321448A1 (de) 2001-12-21 2001-12-21 Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik

Publications (1)

Publication Number Publication Date
EP1321448A1 true EP1321448A1 (de) 2003-06-25

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EP01870291A Withdrawn EP1321448A1 (de) 2001-12-21 2001-12-21 Verfahren zum Verändern der hydrophilen Eigenschaften von keramischen Oxiden oder oxidischer Keramik

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US (1) US20030145749A1 (de)
EP (1) EP1321448A1 (de)
JP (1) JP2003211623A (de)
WO (1) WO2003053882A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102209633B (zh) 2008-09-12 2014-01-22 Jp影像有限公司 制备用于印刷的印刷版前体的方法及设备
US8323803B2 (en) 2009-04-01 2012-12-04 Xerox Corporation Imaging member
EP2547525A1 (de) * 2010-03-18 2013-01-23 J P Imaging Limited Verbesserungen bei oder im zusammenhang mit drucken

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238530A (en) * 1992-04-20 1993-08-24 Texas Instruments Incorporated Anisotropic titanate etch
EP0556966A1 (de) * 1992-02-07 1993-08-25 Zortech International Limited Beschichtung von hydrophobem, mikroporösem, wärmeisolierendem Material
US5965629A (en) * 1996-04-19 1999-10-12 Korea Institute Of Science And Technology Process for modifying surfaces of materials, and materials having surfaces modified thereby

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939194A (en) * 1996-12-09 1999-08-17 Toto Ltd. Photocatalytically hydrophilifying and hydrophobifying material
US5836248A (en) * 1997-05-01 1998-11-17 Eastman Kodak Company Zirconia-alumina composite ceramic lithographic printing member
US5893328A (en) * 1997-05-01 1999-04-13 Eastman Kodak Company Method of controlled laser imaging of zirconia-alumina composite ceramic lithographic printing member to provide localized melting in exposed areas
US5925496A (en) * 1998-01-07 1999-07-20 Eastman Kodak Company Anodized zirconium metal lithographic printing member and methods of use
DE19826377A1 (de) * 1998-06-12 1999-12-16 Heidelberger Druckmasch Ag Druckmaschine und Druckverfahren
US6391522B1 (en) * 1998-10-23 2002-05-21 Fuji Photo Film Co., Ltd. Offset printing plate precursor and method for offset printing using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556966A1 (de) * 1992-02-07 1993-08-25 Zortech International Limited Beschichtung von hydrophobem, mikroporösem, wärmeisolierendem Material
US5238530A (en) * 1992-04-20 1993-08-24 Texas Instruments Incorporated Anisotropic titanate etch
US5965629A (en) * 1996-04-19 1999-10-12 Korea Institute Of Science And Technology Process for modifying surfaces of materials, and materials having surfaces modified thereby

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JP2003211623A (ja) 2003-07-29
US20030145749A1 (en) 2003-08-07
WO2003053882A1 (en) 2003-07-03

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